JPH02275730A - Purification of glass raw material - Google Patents
Purification of glass raw materialInfo
- Publication number
- JPH02275730A JPH02275730A JP9308789A JP9308789A JPH02275730A JP H02275730 A JPH02275730 A JP H02275730A JP 9308789 A JP9308789 A JP 9308789A JP 9308789 A JP9308789 A JP 9308789A JP H02275730 A JPH02275730 A JP H02275730A
- Authority
- JP
- Japan
- Prior art keywords
- chamber
- raw material
- trap
- glass raw
- trap chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 32
- 239000011521 glass Substances 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims description 8
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 239000005387 chalcogenide glass Substances 0.000 abstract description 14
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 239000011669 selenium Substances 0.000 description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- -1 stainless steel Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 description 1
- 229910003846 O-H Inorganic materials 0.000 description 1
- 229910003866 O—H Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は、赤外線透過率の高いカルコゲノ−イドガラス
、特に１〜６μｍの波長領域に於て、Ｓ−Ｈ，５ｅ−Ｈ
，Ｏ−Ｈ等による吸収が小さいカルコゲナイドガラスの
精製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention provides chalcogenoid glasses with high infrared transmittance, particularly S-H, 5e-H in the wavelength range of 1 to 6 μm.
This invention relates to a method for purifying chalcogenide glass with low absorption by , O-H, etc.
［従来の技術１
カルコゲナイドガラスは赤外線透過）？イバー用の材料
どして注目されている。カルコゲナイドガラスの赤外線
透過率を向上させるためには、ガラス原料の選択及び該
ガラスの十分な精製を行う必要があり、従来から種々の
方法が研究されている。中でもイオウ（Ｓ）、セレン（
Ｓｅ）、及びこれらのカルコゲン元素を含有するガラス
の精製には蒸留法が有効である。前記ガラス原料または
ガラス中に含まれる不純物の内、鉄、ニッケル、コバル
ト等の金属不純物や酸素不純物は、原料またはガラスを
真空下、または不活性雰囲気下で蒸留することによって
比較的容易に除去できるが、Ｓ−Ｈ，５ｅ−Ｈ等の水素
化物及び水分（０−１−１）は、通常の蒸留方法では十
分に除去できない。[Conventional technology 1 Chalcogenide glass transmits infrared rays]? It is attracting attention as a material for ivar. In order to improve the infrared transmittance of chalcogenide glass, it is necessary to select glass raw materials and sufficiently purify the glass, and various methods have been studied. Among them, sulfur (S), selenium (
Distillation is effective for purifying glass containing Se) and these chalcogen elements. Among the impurities contained in the glass raw material or glass, metal impurities such as iron, nickel, cobalt, etc. and oxygen impurities can be relatively easily removed by distilling the raw material or glass under vacuum or in an inert atmosphere. However, hydrides such as S-H and 5e-H and water (0-1-1) cannot be sufficiently removed by ordinary distillation methods.
Ｓ−Ｈ，５ｅ−Ｈ等の水素化物及び水分（０）」）を効
率よく除去する手段として、５２ＣＩ２またはＳｅ
ＣｆＪ２等の塩素化合物のガス雰囲気下でＳまたはＳｅ
を蒸留することが知られている（特開昭５８−１２０５
３８１．これは、室温で液体状態のＳ Ｃ１または５ｅ
２（Ｊ２中にアルゴン等の不活性ガスを導入することに
よって発生するＳ２ＣΩ またはＳｅ２ガスの雰囲気下
でＳまたはＳｅを蒸留するという方法であった。52CI2 or Se
S or Se in a gas atmosphere of chlorine compounds such as CfJ2
It is known that distillation of
381. This is S C1 or 5e, which is in a liquid state at room temperature.
2 (J2) was a method in which S or Se was distilled in an atmosphere of S2CΩ or Se2 gas generated by introducing an inert gas such as argon into J2.
［発明が解決しようとする課題］
しかし、上記のような蒸留精製法に用いられる液体状態
の５２Ｃ１２またはＳｅ、、ＣＮ２は極めて不安定な物
質であり、またステンレス等の金属を激しく腐食し、さ
らに有毒で刺激臭を呈するため、使用し得る蒸留装置の
材質が限られるばかりか、蒸留操作が極めて困難であっ
た。また上記精製法で得られるＳまたはＳｅには微ｍの
ハロゲン元素が残存するため、それらを原料に用いてカ
ルコゲナイドガラスを作製すると、ガラスの耐候性、機
械的強度が低下するという欠点があった。[Problems to be Solved by the Invention] However, the liquid 52C12 or Se, CN2 used in the above-mentioned distillation purification method is an extremely unstable substance, severely corrodes metals such as stainless steel, and Because it has a toxic and pungent odor, not only the materials that can be used for distillation equipment are limited, but also the distillation operation is extremely difficult. Furthermore, since minute amounts of halogen elements remain in S or Se obtained by the above purification method, when chalcogenide glass is produced using these as raw materials, there is a drawback that the weather resistance and mechanical strength of the glass are reduced. .
本発明の目的は、蒸留操作が容易で、ハロゲン化物を用
いることなくＳ−Ｈ，５ｅ−Ｈ，Ｏ−Ｈ等の不純物の含
有間が低いカルコゲナイドガラス原料の精製方法及びカ
ルコゲナイドガラスの製造方法を提供することにある。The object of the present invention is to provide a method for purifying a raw material for chalcogenide glass, which is easy to distill, and has a low content of impurities such as S-H, 5e-H, and O-H without using halides, and a method for producing chalcogenide glass. It is about providing.
［課題を解決するための手段］
本発明はガラス原料を容器の中に収納し、該容器内部を
減圧脱気しながら蒸留する精製法において、該容器が融
解室、第１１−ラップ室、第２トラップ室の順に３室に
わかれており、第１ステップとしてＦ！Ｉｌ解室から第
１トラップ卒へ蒸留する工程、第２ステップとして第１
トラップ空から融解室へ逆流させる工程、第３ステップ
として融解室から第２トラップ室へ蒸留する工程を含む
ことを特徴とするガラス原料の精製方法を採用すること
により、」：開目的を達成し得る。[Means for Solving the Problems] The present invention provides a purification method in which a glass raw material is stored in a container and distilled while the inside of the container is degassed under reduced pressure. It is divided into 3 rooms in the order of 2 trap rooms, and the first step is F! The process of distilling from the Il dissolution chamber to the first trap, the second step is the first
By adopting a method for purifying a glass raw material, which is characterized by comprising a step of backflowing from the trap air to a melting chamber, and a step of distilling from the melting chamber to a second trap chamber as a third step, the objective is achieved. obtain.
ここで、各室の温度をＴ 、Ｔ 、Ｔ２とし、原料
の融点をＴ□とし、それぞれのステップにおいて、下記
の温度に設定されていることを特徴としている。Here, the temperature of each chamber is T 1 , T 2 , T2, the melting point of the raw material is T □, and each step is characterized by being set at the following temperature.
すなわち本発明は、カルコゲナイドガラス原料であるイ
オウまたはセレン中に存在する５−ＨｌＳｅ−Ｈ，Ｏ−
Ｈ等の低沸点不純物を除去するために、融解室から第１
トラップ室への蒸留〈第１ステップ）と第１トラップ室
から融解室への該原ｖ１の逆流（第２ステップ）を交互
に複数回くり返した後に融解室から第２トラップ室への
蒸留（第３ステップ）を行うことを特徴としている。ざ
らに第２トラップ室の次に第３トラップ室を加え、第３
トラップ室を上記各ステップに於いて、Ｔｍ−５０〜Ｔ
ｌｌ１−１０の範囲の温度に保つことにより、より収率
を高めることが出来る。That is, the present invention provides 5-HlSe-H,O- present in sulfur or selenium, which is a raw material for chalcogenide glass.
In order to remove low-boiling point impurities such as H, the first
After repeating the distillation into the trap chamber (first step) and the backflow of the source v1 from the first trap chamber to the melting chamber (second step) several times, the distillation from the melting chamber to the second trap chamber (second step) is repeated several times. 3 steps). Roughly add the third trap chamber after the second trap chamber,
The trap chamber was heated to Tm-50 to Tm in each step above.
By maintaining the temperature in the range of 11-10, the yield can be further increased.
本発明において、第１ステップでの王。、第３ステップ
でのＴｏＸＴｌは０、Ｔ１、＋１０〜Ｔ、＋１８０℃の
範囲に設定することが好ましく、上記限定範囲下限より
も低い場合、イオウ、セレンの蒸発に非常に長時間を要
し、生産性が悪い。In the present invention, the king in the first step. It is preferable that ToXTl in the third step be set in the range of 0, T1, +10 to T, +180°C, and if it is lower than the lower limit of the above-mentioned limited range, it will take a very long time to evaporate sulfur and selenium. Poor productivity.
またＴ、Ｔ１が上記限定範囲上限よりも高い温度になる
とイオウまたはセレンの蒸発が速くなりすぎて第１ステ
ップにおｔプる第１トラップ室でのトラップ効率が下が
り、また第３ステップでの第２トラップ室の収率が低下
する。また第２ステップでのＴ、Ｔ１の値はＴｌｌ１＋
１０〜Ｔｌｌ１＋５０の範囲に設定することが存ましく
０、Ｔ１、Ｔ１が上２限定範囲下限よりも低い場合には
イオウまたはセレンが第１トラップ室から融解室へ逆流
することができなかったり、逆流に長時間を要するため
に生産性が悪い場合がある。また第２ステップでのＴ、
Ｔ１が上記限定範囲上限よりも高い温度域になるとイオ
ウまたはセレンの一部が気化して第３トラップ室へ移動
するため、第３ステップでの第２トラップ室における収
率が下がる。Furthermore, if T and T1 become higher than the upper limits of the limited ranges mentioned above, the evaporation of sulfur or selenium becomes too fast, reducing the trapping efficiency in the first trap chamber leading to the first step, and reducing the trap efficiency in the third step. The yield of the second trap chamber is reduced. Also, the values of T and T1 in the second step are Tll1+
It is preferable to set it in the range of 10 to Tll1 + 50. If T1 and T1 are lower than the lower limit of the upper two limited ranges, sulfur or selenium cannot flow back from the first trap chamber to the melting chamber. Productivity may be poor because backflow takes a long time. Also, T in the second step,
When T1 reaches a temperature range higher than the upper limit of the limited range, some of the sulfur or selenium vaporizes and moves to the third trap chamber, resulting in a decrease in the yield in the second trap chamber in the third step.
一方策１ステップ及び第２ステップでのＴｌはＴｌ＞Ｔ
、＋２０℃に設定しておくことかが望ましく、上記限定
範囲下限以下の温度では第２トラップ室内にイオウまた
はセレンがトラップされることがある。さらに第３ステ
ップでのＴｌ及び第１〜第３ステップでのＴ３はＴｌ１
ｌ−５０〜丁。On the other hand, Tl in step 1 and step 2 is Tl>T
, +20°C. At temperatures below the lower limit of the above-mentioned limited range, sulfur or selenium may be trapped in the second trap chamber. Furthermore, Tl in the third step and T3 in the first to third steps are Tl1
l-50 ~ ding.
−１０℃に設定することが好ましい。Ｔｌ、Ｔ３が上記
限定範囲の下限よりも低い温度では、高純度化されたイ
オウ、セレンと同時にＳ−１−１，Ｓｅ−ト１、Ｏ−Ｈ
等も同時にトラップされることがあり、また下２、Ｔ３
が上記限定範囲の上限よりも高い温度に設定すると、第
２、第３トラップ室での収率が下がる場合がある。It is preferable to set the temperature to -10°C. At temperatures where Tl and T3 are lower than the lower limit of the above-mentioned limited range, highly purified sulfur, selenium and S-1-1, Se-to-1, O-H
etc. may be trapped at the same time, and lower 2, T3
If the temperature is set higher than the upper limit of the above-mentioned limited range, the yield in the second and third trap chambers may decrease.
本発明で使用するガラス容器は石英ガラスが好ましく、
特に無水石英ガラスが望ましい。これは通常の石英ガラ
スの場合、ガラス中に存在する水分が該カルコゲナイド
ガラス原料中に拡散して原料を汚染する場合があるから
である。The glass container used in the present invention is preferably quartz glass,
Anhydrous quartz glass is particularly desirable. This is because, in the case of ordinary quartz glass, water present in the glass may diffuse into the chalcogenide glass raw material and contaminate the raw material.
また本発明に於いて、石英容器内で加熱、熔融されたイ
オウまたはセレンを真空下で蒸留する際の容器内の圧力
は１０ ’ｔｏｒｒ以下であることが好ましい。容器内
の圧力が１０ ’ｔｏｒｒよりも高い場合、該カルコゲ
ナイドガラス原料を蒸留する際の蒸留温度を高くする必
要があり、Ｓ−Ｈ，Ｓｅト１、Ｏ−Ｈの除去効率が低下
する場合がある。Further, in the present invention, when sulfur or selenium heated and melted in a quartz container is distilled under vacuum, the pressure inside the container is preferably 10'torr or less. If the pressure inside the container is higher than 10' torr, it is necessary to increase the distillation temperature when distilling the chalcogenide glass raw material, and the removal efficiency of S-H, Se, and O-H may decrease. be.
更に本発明によって精製されたイオウまたはセレンとＧ
ｅｌＡｓ％Ｔｅ、５ｂＳＴｊおよびハロゲンから選ばれ
た１種または２種以上の原料を混合熔融してロンド状と
し、これを紡糸してカルコゲナイドガラスファイバーを
作ることができる。Furthermore, sulfur or selenium purified according to the present invention and G
A chalcogenide glass fiber can be produced by mixing and melting one or more raw materials selected from elAs%Te, 5bSTj, and halogen to form a rond shape, and spinning this into a rond shape.
［実 施 例１ 次に本発明の詳細な説明する。[Implementation Example 1] Next, the present invention will be explained in detail.
実施例１
第１図はこの実施例で用いた精製のための無水石英ガラ
ス容器の断面図である。ここで１はカルコゲナイドガラ
ス原料を融解するための融解室、２は第１トラップ室、
３は第２トラップ室、４は第３トラップ室、モして５は
真空脱気口である。Example 1 FIG. 1 is a sectional view of an anhydrous quartz glass container for purification used in this example. Here, 1 is a melting chamber for melting the chalcogenide glass raw material, 2 is a first trap chamber,
3 is a second trap chamber, 4 is a third trap chamber, and 5 is a vacuum degassing port.
まず融解室１ヘカルコゲナイドガラス粗原料である市販
品の６Ｎの塊状イオウを入れ、石英ガラス容器内を１０
”６ｔｏｒｒ以下に真空脱気した。その侵第１トラッ
プ室２を１００℃、第２トラップ室３を２００℃、第３
トラップ室４を１００℃に昇温して、融解室１をゆっく
り １８０℃まで昇温した（第１ステップ）。融解室内
のイオウがすべて蒸発したことを確認してから融解室１
と第１トラップ室２とを１５０℃に、第２、第３トラッ
プ３．４室はそのままの温度に保らながら第１トラップ
室内のイオウを融解室１へ逆流させたく第２ステップ）
。第１ステップと第２ステップとを交互に４回くり返し
！ζ後に、第２、第３トラップ室３．４を １００℃に
保ら、かつ第１トラップ室２及び＠前室１を１８０℃ま
で昇温したく第３ステップ）。この様にして第２トラッ
プ室に集められたイオウを用いて外径４００μｍのＡＳ
４ｏＳ６ｏガラスファイバーを作製し、その透過ｎ失を
測定したところ第２図に示す様に４．１μｍのＳ−［」
の吸収ピークは２．４ｄＢ／ ｍ以下であり、また３、
ｃｚｍ付近のＯ−Ｈの吸収ピークは０．７ｄＢ／ｍ以下
であった。First, a commercially available 6N lump of sulfur, which is a crude raw material for hechalcogenide glass, is placed in the melting chamber 1, and the inside of the quartz glass container is heated to 10%.
"The vacuum was degassed to 6 torr or less. The first trap chamber 2 was heated to 100°C, the second trap chamber 3 was heated to 200°C, and the third
The temperature of the trap chamber 4 was raised to 100°C, and the temperature of the melting chamber 1 was slowly raised to 180°C (first step). After confirming that all the sulfur in the melting chamber has evaporated, open the melting chamber 1.
and the first trap chamber 2 at 150°C, and the second and third trap chambers at the same temperature (3.4), it is desired to cause the sulfur in the first trap chamber to flow back into the melting chamber 1).
. Repeat the first step and second step 4 times alternately! After ζ, it is desired to maintain the second and third trap chambers 3.4 at 100° C., and raise the temperature of the first trap chamber 2 and @front chamber 1 to 180° C. (third step). Using the sulfur collected in the second trap chamber in this way, an AS with an outer diameter of 400 μm was prepared.
A 4oS6o glass fiber was prepared and its transmission n loss was measured, and as shown in Fig. 2, a 4.1 μm S-[''
The absorption peak of is less than 2.4 dB/m, and 3,
The O-H absorption peak near czm was 0.7 dB/m or less.
実施例２
実施例１と同じ形の石英ガラス容器を用いて市販の純度
６Ｎの粒状セレンを実施例１と同じ手順で精製した。た
だし、第１〜第３ステップでの融前室、第１〜第３トラ
ップ室の各温度は以下に示す様に設定した。Example 2 Using a quartz glass container of the same shape as in Example 1, commercially available granular selenium with a purity of 6N was purified in the same manner as in Example 1. However, the temperatures of the pre-melting chamber and the first to third trap chambers in the first to third steps were set as shown below.
この様にして第２トラップ室に集められたセレンを用い
て外径４００μｍのＧｅ２ｏＳｅ８ｏガラスフアイバー
を作製し、その透過損失を測定したところ、第３図に示
す様に４．５μｍ付近の５ｅ−Ｈに起因するピークは約
２ ｄＢ／ ｍまた３μｍ付近の０−Ｈの吸収ピークは
０．６ｄＢ／ ｍ下であった。A Ge2oSe8o glass fiber with an outer diameter of 400 μm was fabricated using the selenium collected in the second trap chamber in this way, and its transmission loss was measured. As shown in Figure 3, the 5e-H The peak due to 0-H was about 2 dB/m, and the 0-H absorption peak near 3 μm was 0.6 dB/m.
比較例−１
第４図に示す石英容器を用いて市販の６Ｎの塊状イオウ
を蒸留した。ここで１は融解室、２はトラップ室、３は
真空脱気口である。まず融解室１へ市販６Ｎイオウを入
れ、石英ガラス容器内を１０’ｔｏｒｒ以下に真空脱気
し、融解室を１８０℃に、トラップ室を１００℃に譬温
した。この様にしてトラップ室内に集められたイΔつを
用いて外径４００μｍのΔ５４０Ｓ６０ファイバーを作
製した。Comparative Example-1 Commercially available 6N bulk sulfur was distilled using a quartz container shown in FIG. Here, 1 is a melting chamber, 2 is a trap chamber, and 3 is a vacuum degassing port. First, commercially available 6N sulfur was charged into the melting chamber 1, the inside of the quartz glass container was vacuum degassed to 10'torr or less, and the melting chamber was heated to 180°C and the trap chamber to 100°C. A Δ540S60 fiber with an outer diameter of 400 μm was produced using the Δ fibers collected in the trap chamber in this manner.
得られたファイバーの透過損失を第５図に示す。The transmission loss of the obtained fiber is shown in FIG.
４、ｉμ？１ＬのＳ−１−１の吸収及び３μｍ付近のＯ
−Ｈの吸収はＳ −１−１が８ｄＢ／ｍ、Ｏ−Ｈが３．
２ｄＢ／ｍであった。4.iμ? Absorption of 1 L of S-1-1 and O near 3 μm
-H absorption is 8 dB/m for S -1-1 and 3.
It was 2 dB/m.
比較例−２
第４図に示″ｔＪ無水石英ガラス容器を用いて比較例−
１と同じ手順で市販の６ＮａＳｅを蒸留した。Comparative Example-2 Comparative Example using the tJ anhydrous quartz glass container shown in Figure 4-
Commercially available 6NaSe was distilled using the same procedure as in 1.
ただし、融解室１は３２０℃に、またトラップ２室は１
２０℃に保った。このようにして得られたＳ○を用いて
Ｇ ０２０Ｓ ｅ Ｈガラスファイバーを作製し、その
透過損失を測定したところ、第６図に示ず様に４．５μ
ｍの３ ｅ −１−１の吸収、３μｍ付近の○ト１の吸
収はそれぞれ１１ ｄＢ／ ｍ、２ｄＢ／ｍｒあった。However, melting chamber 1 is heated to 320℃, and trap 2 chamber is heated to 1
It was kept at 20°C. A G 020S e H glass fiber was manufactured using the S○ obtained in this way, and its transmission loss was measured, and as shown in Figure 6, it was 4.5μ.
The absorption of 3e-1-1 of m and the absorption of ○1 of around 3 μm were 11 dB/m and 2 dB/mr, respectively.
［発明の効果］
本発明の方法によれば、毒性及び強い腐食性をす５Ｃｆ
１２またはは５ｅ２Ｃ１２を用いることなく、赤外線透
過率の高いカルコゲナイドガラス、特に、１−５μｍの
波長領域に於て強い吸収を示ｔ Ｓ −１−１、Ｓ ｅ
−）−１、Ｏ−Ｈ等の不純物濃度が低いカルコゲナイ
ドガラスを容易に製造することができる。[Effect of the invention] According to the method of the invention, 5Cf, which is toxic and highly corrosive, can be
Chalcogenide glass with high infrared transmittance without using 12 or 5e2C12, especially showing strong absorption in the wavelength region of 1-5 μm t S -1-1, S e
-)-1, chalcogenide glass with a low concentration of impurities such as O-H can be easily produced.
第１図は本発明の実施例で使用した無水石英ガラスの精
製容器の側面図、第２図および第３図は本発明によって
Ｐｌられたファイバーの透過損失線図、第４図は従来例
として比較例で使用した無水石英ガラスの精製容器の側
面図、第５図および第６図は比較例−１〜２で得られた
ファイバーの透過１０失線図である。
第２図
２ ４ ６ ８ ＋０ １２
１長 （μｍ）
１・・・融解室、２・・・第１トラップ室、３・・・第
２トラップ室、４・・・第３トラップ室、５・・・真空
脱気口。Fig. 1 is a side view of an anhydrous quartz glass purification vessel used in an example of the present invention, Figs. 2 and 3 are transmission loss diagrams of a fiber Pl according to the present invention, and Fig. 4 is a conventional example. A side view of the anhydrous quartz glass purification container used in the comparative example, and FIGS. 5 and 6 are transmission 10-loss diagrams of the fibers obtained in comparative examples 1 and 2. Fig. 2 4 6 8 +0 12 1 Length (μm) 1... Melting chamber, 2... First trap chamber, 3... Second trap chamber, 4... Third trap chamber, 5... ...Vacuum deaeration port.
Claims (1)
脱気しながら蒸留する精製法において、該容器が融解室
、第１トラップ室、第２トラップ室の順に３室にわかれ
ており、第１ステップとして融解室から第１トラップ室
へ蒸留する工程、第２ステップとして第１トラップ室か
ら融解室へ逆流させる工程、第３ステップとして融解室
から第２トラップ室へ蒸留する工程を含むことを特徴と
するガラス原料の精製方法。 ２ 各室の温度をＴ＿０、Ｔ＿１、Ｔ＿２とし、原料の
融点をＴ＿ｍとし、それぞれのステップにおいて、下記
の温度に設定されていることを特徴とする請求項１記載
のガラス原料の精製方法。 ▲数式、化学式、表等があります▼ ３ 第２トラップ室の次に第３トラップ室を加え、第３
トラップ室を上記各ステップに於いて、Ｔ＿ｍ−５０〜
Ｔ＿ｍ−１０の範囲の温度に保つことを特徴とする請求
項１または２記載のガラス原料の精製方法。 ４ 該第１ステップと該第２ステップとの間を少なくと
も、２回以上繰り返すことを特徴とする請求項１記載の
ガラス原料の精製方法。 ５ 該容器が無水石英ガラスであり、且つ蒸留中の該容
器内の圧力が１０ｔｏｒｒ以下であることを特徴とする
請求項１記載のガラス原料の精製方法。 ６ ガラス原料がＳ又はＳｅであることを特徴とする請
求項１記載ガラス原料の精製方法。[Claims] 1. A purification method in which a glass raw material is stored in a container and distilled while the inside of the container is degassed under reduced pressure, wherein the container has three melting chambers, a first trap chamber, and a second trap chamber in this order. The first step is distillation from the melting chamber to the first trap chamber, the second step is backflow from the first trap chamber to the melting chamber, and the third step is from the melting chamber to the second trap chamber. A method for refining glass raw materials, characterized by including a step of distilling. 2. The method for refining glass raw materials according to claim 1, wherein the temperature of each chamber is T_0, T_1, T_2, the melting point of the raw material is T_m, and the following temperatures are set in each step. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 3 Add the third trap chamber after the second trap chamber, and
The trap chamber was heated to T_m-50~ in each of the above steps.
The method for refining glass raw materials according to claim 1 or 2, characterized in that the temperature is maintained in the range of T_m-10. 4. The method for refining a glass raw material according to claim 1, wherein the step between the first step and the second step is repeated at least twice. 5. The method for refining a glass raw material according to claim 1, wherein the container is made of anhydrous quartz glass, and the pressure inside the container during distillation is 10 torr or less. 6. The method for refining a glass raw material according to claim 1, wherein the glass raw material is S or Se.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1093087A JPH0813690B2 (en) | 1989-04-14 | 1989-04-14 | Purification method of chalcogenide glass raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1093087A JPH0813690B2 (en) | 1989-04-14 | 1989-04-14 | Purification method of chalcogenide glass raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02275730A true JPH02275730A (en) | 1990-11-09 |
| JPH0813690B2 JPH0813690B2 (en) | 1996-02-14 |
Family
ID=14072745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1093087A Expired - Lifetime JPH0813690B2 (en) | 1989-04-14 | 1989-04-14 | Purification method of chalcogenide glass raw material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813690B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018177565A (en) * | 2017-04-07 | 2018-11-15 | 日本電気硝子株式会社 | Chalcogenide glass |
-
1989
- 1989-04-14 JP JP1093087A patent/JPH0813690B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018177565A (en) * | 2017-04-07 | 2018-11-15 | 日本電気硝子株式会社 | Chalcogenide glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813690B2 (en) | 1996-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FR2582019A1 (en) | PROCESS FOR THE PRODUCTION OF METALS BY REDUCING METAL SALTS, METALS THUS OBTAINED AND DEVICE FOR IMPLEMENTING THE SAME | |
| JP2003525197A (en) | Process for producing crystals and / or crystalline materials free of undesirable impurities and the use of such crystals | |
| CN1148266A (en) | Removal of metal impurities on the surface of polysilicon | |
| CN116161629B (en) | A method for purifying selenium | |
| JPH0717704A (en) | Refining method of silicon by electron beam melting | |
| JP2004531444A (en) | Preparation method of fluoride single crystal | |
| Pearson et al. | The behaviour of metals, particularly lead and bismuth, in atomic hydrogen, and attempts to prepare atomic hydrogen from hydrides | |
| JP2001240497A (en) | Method and equipment for manufacturing single crystal fluoride | |
| JPH0813690B2 (en) | Purification method of chalcogenide glass raw material | |
| WO2022103295A1 (en) | Method for producing high-purity metallic scandium | |
| US4801442A (en) | Method for purifying starting materials for fabricating chalchogenide glass | |
| JPH0444618B2 (en) | ||
| JPH02124742A (en) | Method for refining starting material for chalcogenide glass | |
| JP2520767B2 (en) | Method for manufacturing chalcogenide glass | |
| JPS62265105A (en) | Method and device for purifying chalcogenide material | |
| US3301660A (en) | Metal purification process | |
| RU2852018C1 (en) | Device for deep purification of metals | |
| US2931709A (en) | Decarburizing silicon tetrachloride | |
| JPS58120538A (en) | Production of chalcogenide glass | |
| JP4335026B2 (en) | Process for producing bromine-rich thallium bromide single crystals | |
| CN118771721A (en) | A kind of Si-containing chalcogenide glass and its preparation method and application | |
| JP2000351696A (en) | Method for producing bulk single crystal of fluoride | |
| UA150010U (en) | METHOD OF REFINING METAL OR ITS COMPOUNDS FROM CHEMICAL AND RADIOACTIVE IMPURITIES U, Th, <sup> 40 </sup> K | |
| JPS6241184B2 (en) | ||
| JPS6163515A (en) | Production of monosilane |